ARTICLE
Effect of Temperature on the
Capacitance of Carbon Nanotube
Supercapacitors
Charan Masarapu, Hai Feng Zeng, Kai Hsuan Hung, and Bingqing Wei*
Department of Mechanical Engineering, University of Delaware, Newark, Delaware 19716
upercapacitors are becoming attrac-
S tive power sources in memory backup
devices, electric vehicles, military
weapons, space equipment, and in a num-
ber of day-to-day electronic equipment.1⫺4
Especially for military, space, and electric ve-
hicle applications, supercapacitors with
high energy and power densities that can
withstand harsh temperature environments
are extremely desirable. To design a super-
capacitor for a specific application that re-
quires high energy density or high power
density or both, proper electrode materials
and a suitable electrolyte are to be chosen.
For this purpose, it is of utmost importance
to have the fundamental understanding of
the interface properties of the electrode/
electrolyte, such as the interface structure,
charge transfer, ion diffusion, etc., which
play a vital role in governing the rate capa-
bility and specific capacitance of the super-
capacitor. Cyclic voltammetry (CV) and elec-
trochemical impedance spectroscopy (EIS)
are some of the powerful characterization
techniques that have the capability to
throw light on such electrode/electrolyte
properties in a supercapacitor assembly.
Carbon, in its various forms, is currently
the most extensively examined and widely
utilized electrode material in
supercapacitors.5⫺7 While extensive work
has been done in understanding the kinet-
ics and diffusion mechanism of ions in the
activated carbons8,9 and in nanosized car-
bon materials10,11 at room temperature, very
little research has been realized on the
temperature-dependent studies. Organic
electrolytes in general have wide voltage
windows of operation and high decomposi-
tion temperatures, compared to aqueous
electrolytes.12⫺15 Until recently, the
temperature-dependent studies on super-
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ABSTRACT The effect of temperature on the kinetics and the diffusion mechanism of the ions in a
supercapacitor assembled with single-walled carbon nanotube (SWNT) film electrodes and an organic electrolyte
were thoroughly investigated. An improved room temperature performance of the supercapacitor was observed
due to the combined effects of an increase in the conductivity of the SWNT films and surface modifications on the
SWNT films by repeatedly heating and cooling the supercapacitor between the temperatures of 25 and 100 °C.
Modified Randles equivalent circuit was employed to carry out an extensive analysis of the Nyquist spectra
measured at different temperatures between 25 and 100 °C in order to understand the fundamentals of the
capacitive and resistive variations in the supercapacitor. The experimental results and their thorough analysis
will have significant impact not only on the fundamental understanding of the temperature-dependent electrode/
electrolyte interfacial properties but also on supercapacitor design with appropriate electrode materials for
numerous industrial and consumer applications. The supercapacitor with SWNT film electrodes was capable of
withstanding current densities as high as 100 A/g, yielding eminent specific power density values of about 55 kW/
kg. Ultralong galvanostatic chargeⴚdischarge cycling over 200 000 cycles with a constant current density of 20 A/
g at 25 and 100 °C, respectively, showed excellent stability in capacitance with more than 80% efficiency. The
usage of such a supercapacitor potentially enables far-reaching advances in backup energy storage and high pulse
power applications.
KEYWORDS: single-walled carbon nanotube · temperature
effect · supercapacitor · impedance spectroscopy · ionic diffusion
capacitors assembled with conventional
carbonaceous materials in an organic elec-
trolyte have been limited to around 70
°C.16,17 However, these studies did not ad-
dress the effects of rigorous temperature
conditions such as the repeated heating
and cooling, continuous high temperature,
etc. on the supercapacitor performance,
which are practically important for commer-
cial applications. Moreover, there has been
no systematic work on the temperature ef-
fects on the nanosized carbon electrodes in *Address correspondence to
weib@udel.edu.
supercapacitors compared with the con-
ventional carbonaceous materials. Received for review May 14, 2009
Carbon nanotubes (CNTs), with their and accepted July 01, 2009.
unique architecture,18 excellent conductiv-
Published online July 7, 2009.
ity,19 and high surface area20 have drawn 10.1021/nn900500n CCC: $40.75
significant attraction as nanosized superca-
pacitor electrodes.21,22 Rate capability © 2009 American Chemical Society
VOL. 3 ▪ NO. 8 ▪ 2199–2206 ▪ 2009 2199
ARTICLE
Figure 1. Photographs illustrating the free-standing SWNT electrode
preparation process. (a) Purified SWNT film on water surface. (b) Free-
standing SWNT film on the wire loop. (c) Electrodes with 1.25 cm diam-
eter punched from the free-standing SWNT film. (d) SWNT film on the wire
loop after punching the electrodes. (e) Schematic representation of the su-
percapacitor coin cell assembly with the free-standing SWNT films with-
out any current collectors. A Teflon O-ring was used to seal the coin cell to
perform high-temperature measurements up to 100 °C.
studies determine the rate at which the supercapacitor
can be charged and discharged. Extremely high rate ca-
pabilities can be achieved by utilizing CNT electrodes
in supercapacitors when compared to the conventional
carbonaceous materials.23,24 Especially the single-walled
carbon nanotubes (SWNTs) can be synthesized as long
tube structures25 that are favorable for preparing en-
tangled mats of free-standing electrodes with the filtra-
tion technique.26 The free-standing films can be used di-
rectly as electrode materials without any complex
nanotube coating procedures,27 and there is no require-
ment for the current collector. The supercapacitors as-
sembled with such free-standing SWNT films have
shown good capacitance stability and high rate capabil-
ity and yielded reasonable specific capacitance values
at room temperature in both aqueous and organic
electrolytes.28⫺31
Here, we report the temperature effects of a coin
cell supercapacitor assembled with free-standing SWNT
film electrodes and tetraethylammonium
tetrafluoroborate⫺polypropylene carbonate (TEABF4/
PC) electrolyte under rigorous temperature conditions
(25⫺100 °C). Unlike the filtration technique, where the
nanotubes are dispersed in a solution and filtered to ob-
tain the free-standing SWNT films,26 we utilized the
SWNT films directly synthesized by a chemical vapor
deposition (CVD) method reported elsewhere32 with
post-purification techniques that did not involve a com-
plex filtration process to prepare the electrodes. Electro-
chemical characterization techniques, cyclic voltamme-
try, and the electrochemical impedance spectroscopy
2200 VOL. 3 ▪ NO. 8 ▪ MASARAPU ET AL.
were used to extensively analyze the electrode/electro-
lyte interface properties in the supercapacitor with re-
spect to changes in the temperature. Effects of re-
peated heating and cooling on the performance of the
supercapacitor was studied and compared to the re-
sults of the supercapacitor with activated carbon fab-
ric.33 In addition, ultralong cycle galvanostatic
charge⫺discharge has been carried out at tempera-
tures 25 and 100 °C with repeated heating and cooling
to demonstrate the long-term stability of the superca-
pacitor with the SWNT film electrodes.
RESULTS AND DISCUSSION
Figure 1 shows the electrode preparation from the
free-standing SWNT films and the schematics of a su-
percapacitor cell assembly (detailed information can be
found in the Methods section). The cyclic voltammo-
grams (CVs) of the cell were measured in the voltage
window of ⫺1.5 to ⫹1.5 V (actual potential of opera-
tion is 1.5 V) with scan rates of 50, 100, 200, 500, and
1000 mV/s at each set of temperatures, 25, 50, 75, and
100 °C (Supporting Information, Figure S1). Figure 2a,b
displays the CVs measured at 50 and 1000 mV/s at 25,
100, and 25 °C after cooling back from 100 °C. The vol-
tammograms were close to rectangular shape at 50
mV/s as well as at a very high scan rate of 1000 mV/s, in-
dicating ideal capacitive behavior within this wide tem-
perature window. Figure 2c shows the capacitance val-
ues of the cell calculated from the voltammograms
(Supporting Information S1) measured at different tem-
peratures and plotted with respect to the scan rate.
Interesting results can be observed from these fig-
ures. An increasing pseudocapacitive behavior in the
voltammograms was observed with the increase in the
temperature from 25 to 100 °C, similar to perfectly re-
versible Faradaic reactions taking place in the capaci-
tor. Generally, the Faradaic process involves the elec-
tron transfer across the double layers with a consequent
change of oxidation state, and the measurable capaci-
tance arising due to this process is designated as a
pseudocapacitance. In Figure 2a,b, the pseudocapaci-
tive behavior is indicated by the ovals. The capacitance
at all scan rates gradually increased with the increase
in temperature (Figure 2c). Figure 2c also illustrates the
performance of the cell with repeated heating and cool-
ing. The value of the capacitance at all scan rates ob-
tained at 25 °C after cooling back from 100 °C has a
slight increase (about 10%) compared to the capaci-
tance values obtained initially at the same tempera-
ture of 25 °C. In the present experiment, the maximum
potential was limited to 1.5 V during the CV measure-
ments, but as the cell is being heated, even though the
potential is within the safe decomposition limit of the
PC electrolyte,12 some electrolyte will evaporate and in-
creases the vapor pressure inside the cell. The trace
amount of evolved gases from the electrolyte
system34,35 modifies the surface of the SWNT electrode,
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Figure 2. Cyclic voltammograms of the cell at different tem-
peratures with various scan rates: (a) 50 and (b) 1000 mV/s.
The ovals represent pseudocapacitive behavior in the
voltammograms with perfectly reversible Faradaic reac-
tions taking place in the capacitor. The pseudocapacitive be-
havior is present in the CVs at 25 °C even after cooling from
100 °C. (c) Capacitance of the cell calculated from CVs at dif-
ferent scan rates and at different temperatures versus the
scan rate. Also illustrated is the capacitance of the cell with
repeated heating and cooling between 25 and 100 °C. Due to
the introduction of Faradaic reactions, an increase in the ca-
pacitance is observed at high temperature.
which possibly leads to the physisorbtion of the electro-
lyte ions at high temperature, giving rise to the Fara-
daic currents in the CVs (Figure 2a,b) and causing an in-
crease in the capacitance when heated from 25 to 100
°C (Figure 2c). The surface modification of the SWNT
films is partially irreversible, and the physisorbtion re-
mains even at 25 °C (refer to the ovals in Figure 2a,b) af-
ter cooling from 100 °C. This is evidenced by the CV
curve which shows the pseudocapacitive behavior with
a capacitance value obtained at 25 °C, slightly higher
than the previously obtained value at the same temper-
ature of 25 °C (Figure 2c). The effects of this phenom-
enon on the values of the capacitance can be further ex-
plained in detail by the electrochemical impedance
spectroscopy (EIS) measurements presented in the sub-
sequent paragraphs.
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ARTICLE
The principle objective of the EIS measurements is
to gain insight into the temperature dependence of
the resistive and capacitive elements and their effects
on the performance of the supercapacitor. Figure 3a
shows the Nyquist spectra in the frequency range of
100 kHz to 10 mHz measured at equilibrium open cir-
cuit potential (⬃0 V) at different temperatures from 25
to 100 °C with repeated heating and cooling. The
Nyquist spectrum can be represented by a modified
Randles circuit36 with a set of resistors and capacitors
in series and parallel as shown in Figure 3b. The first in-
tersection point on the real axis of the Nyquist spec-
trum in the high-frequency region provides the value
of the ohmic resistance of the electrolyte and the inter-
nal resistance of the electrode materials and is repre-
sented as RS. The semicircle in the high-frequency re-
gion to midfrequency is modeled by an interfacial
charge transfer resistance RCT and the double layer ca-
pacitance CDL connected parallel to each other. After
the semicircle, the Nyquist spectrum shows a long tail
in the low-frequency region pertaining to the diffusion
of ions into the bulk of the electrode. The transition
from the high-frequency semicircle to the midfre-
quency tail is represented by the Warburg element Wo,
which is expressed as A/(j␻)n, where A is called the War-
burg coefficient, ␻ is the angular frequency, and n is
an exponent. At very low frequencies, an ideally polar-
izable capacitance would give rise to a straight line par-
allel to the imaginary axis with a mass capacitance rep-
resented as CL. However, from Figure 3a, it can be
observed that the spectra obtained at low-frequency
range (⬃1 Hz to 10 mHz) are inclined at an angle to the
real impedance axis, suggesting that a resistive ele-
ment is associated with CL. This resistance can be desig-
nated as the low-frequency leakage resistance Rleak
and is placed parallel to CL in the equivalent circuit. Fig-
ure 3c shows the Nyquist spectra measured at differ-
ent temperatures plotted on a shifted real axis empha-
sizing the high-frequency semicircle and the
midfrequency spike (100 kHz to 1 Hz).
To obtain all of the equivalent circuit parameters,
the fitting of the impedance expression obtained from
the equivalent circuit to the experimental Nyquist spec-
tra in the whole frequency range from 100 kHz to 10
mHz was performed using the EIS data fitting program
ZVIEW. All of the fitting parameters of the Nyquist spec-
tra at all temperatures are shown in the table format
in Figure 3d. The value of RS is significantly decreased
with the increase in the temperature from 25 to 100 °C.
The decrease is caused by an increase in the conductiv-
ity of the electrolyte due to the enhanced mobility of
the ions in the electrolyte with the increase in the tem-
perature but is not contributed by the intrinsic temper-
ature dependence of the SWNTs themselves. This is
verified by measuring the variation in the resistance of
the SWNT film from 25 to 100 °C without the involve-
ment of the electrolyte. Similar to the SWNT bundles,
VOL. 3 ▪ NO. 8 ▪ 2199–2206 ▪ 2009 2201
ARTICLE
Figure 3. Electrochemical impedance spectroscopy measurements on the su-
percapacitor at different temperatures with repeated heating and cooling. (a)
In the frequency range from 100 kHz to 10 mHz. (b) Randles equivalent cir-
cuit representing the circuit elements in the Nyquist spectra. The equivalent
circuit is used to fit the Nyquist spectra using the software ZVIEW. (c) High-
frequency response of the Nyquist spectra of panel a showing the semicircles
plotted on the shifted real axis for clarity. (d) Equivalent circuit parameters
obtained from the fitting results. The performance of the cell when cooled
back to 25 °C improved due to betterment of RS, RCT, CDL, and Wo values com-
pared to the as-assembled cell at 25 °C.
which act as metallic conductors at ambient tempera-
tures,37 the resistance of the SWNT film increased by
about 8% at 100 °C compared to the value at 25 °C (con-
ductivity is about 0.2 S/cm at 25 °C).
The physisorbtion of the electrolyte ions on the
SWNT electrodes with the increase in the temperature
can be explained based on the variations in the values
of CDL and RCT. At high frequencies, the double layer ca-
pacitance CDL arises from the charges present close to
the surface of the SWNT film that overcome the energy
to migrate with the alternating potential. The surface
modification of the SWNTs by the evolved gases from
the electrolyte presumably provides more accessible
sites for the mobile charges near the surface of the
SWNT electrode thus leading to an increase in the value
of CDL from 3 ␮F at 25 °C to 28 ␮F at 100 °C. Also, the
value of the CDL obtained at 25 °C after cooling from 100
°C is higher than the value obtained at 25 °C before
heating. So it should be obvious that the physisorb-
tion is taking place even at 25 °C after cooling back from
100 °C. RCT actually represents the resistance of the
charges in the pores of the SWNT electrode. A reduc-
tion in the value of RCT implies that the surface modifi-
2202 VOL. 3 ▪ NO. 8 ▪ MASARAPU ET AL.
cation is also increasing the conductivity of the SWNT
films. This is evident from the lower values of the RCT at
25 °C after cooling from 100 °C, compared to the val-
ues obtained at 25 °C before heating from the fitting pa-
rameters in Figure 3d.
Some of the important features of the CVs in Figure
2 can also be explained based on the fitting param-
eters in Figure 3d. Generally, the Warburg element rep-
resents the diffusion of ions into the pores on the sur-
face of the electrode during the transition from the
high-frequency semicircle to the midfrequency spike.
Porous electrodes such as activated carbons generate
an exponent value of n ⫽ 0.5, where the spike is at an
angle of 45° to the real axis at room temperature.38 For
the case of SWNTs in this study, it can be observed that
the value of n is 0.6 at 25 °C with the spike near verti-
cal to the real impedance axis yielding an ideal capaci-
tive behavior. The higher value of the exponent indi-
cates that the ion diffusion is taking place only on the
surface of the SWNT electrode and suggests that the
SWNTs are not behaving as typical porous electrodes,33
which is evident from the BET surface area measure-
ments on the SWNT films (see Supporting Information
S3 and Figure S2). Also, the transition from the high-
frequency semicircle to the midfrequency spike as
shown in Figure 3c is occurring at relatively higher fre-
quency of ⬃221 Hz in the case of SWNTs compared to
porous carbon electrodes.23,33 The high rate capability
of the SWNT film supercapacitor compared to the po-
rous electrodes is the direct consequence of the surface
diffusion effects with high exponent values in the War-
burg element and a higher transition frequency from
the semicircle to the vertical spike. Therefore, the CVs
do not deviate much from the rectangular shape even
at a scan rate as high as 1000 mV/s in the case of the su-
percapacitor with carbon nanotube electrodes. Even
though the rate capability is high for carbon nanotube
electrodes, the nonporous nature and the surface diffu-
sion effects limit the number of ions that form the
double layer at the electrode surface and yield lower
gravimetric capacitance compared to the capacitor em-
ploying an activated carbon material.33
With an increase in the temperature from 25 to 100
°C, the value of n is increasing and the Warburg coeffi-
cient A is decreasing. This leads to a better rate capabil-
ity of the supercapacitor at high temperature and is evi-
dent from the loop obtained at 100 °C, which is more
rectangular than the loop obtained at 25 °C with a scan
rate of 1000 mV/s in Figure 2b. However, it is interest-
ing to note from the impedance data of Figure 3c that
the variation of temperature does not lead to any shift
in the frequency of the transition from the high-
frequency semicircle to the midfrequency spike which
is occurring at ⬃221 Hz. This behavior suggests that
there is no time dependence in the charging process
on temperature variation, and the physisorbtion of the
electrolyte ions on the surface of the SWNT films at high
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 ARTICLE
Figure 4. Long cycle galvanostatic chargeⴚdischarge studies on the supercapacitor measured at 25 and 100 °C with differ-
ent current densities from 10 to 100 A/g. Chargeⴚdischarge curve obtained with a constant current density of 10 A/g at (a)
25, (b) 100, and (c) 25 °C after cooling from 100 °C. (d) Chargeⴚdischarge curve obtained with a constant current density of
100 A/g at 100 °C. (e) Long cycle discharge capacitance with a constant current density of 10 A/g at 25 and 100 °C with re-
peated heating and cooling. (f) Long cycle discharge capacitance with current densities of 50 and 100 A/g measured at 25 and
100 °C. (g) Ragone chart of the supercapacitor obtained from the discharge curves measured at different constant current
densities at 25 and 100 °C. (h) Displaying the ultralong cycling stability of the cell by running 246 700 and 224 000 cycles of
chargeⴚdischarge with a current density of 20 A/g at 25 and 100 °C. (i) Cell resistance variations in the coin cell at different
stages of the chargeⴚdischarge measurements.

temperature (Figure 2) is happening at a fast rate with-
out affecting the rate capability. From Figure 3d, the pa-
rameters are getting better at 25 °C with repeated heat-
ing and cooling thus leading to an improved
performance at 25 °C after cooling from 100 °C com-
pared to the performance of the as-assembled superca-
pacitor at 25 °C.
At very low frequency, the mass capacitances esti-
mated from the fitting parameters in Figure 3d are com-
parable to the values obtained from CVs measured at
the scan rate of 50 mV/s (Figure 2c) showing the valid-
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ity of the fitting parameters. The low-frequency leak-
age resistance of the cell is decreasing from 38 k⍀ at ini-
tial 25 °C to about 8 k⍀ at 100 °C. Lower leakage
resistance implies a higher leakage current that causes
the cell to self-discharge faster.16 Considering the varia-
tion of the overall parameters in Figure 3d, the perfor-
mance of the supercapacitor coin cell with SWNT elec-
trodes at 25 °C is improving with repeated heating and
cooling. Such kind of improvement in the performance
was not observed in case of the supercapacitor with ac-
tivated carbon fabric electrodes.33
VOL. 3 ▪ NO. 8 ▪ 2199–2206 ▪ 2009 2203
ARTICLE The improvement in the supercapacitor perfor-
mance with SWNTs with repeated heating and cooling
is further elucidated by the constant current
charge⫺discharge cycling on the supercapacitor (see
Supporting Information S4 for a sequence of
charge⫺discharge measurements). Figure 4a⫺c shows
typical charge⫺discharge curves of the supercapacitor
at initial 25 °C, when heated to 100 °C and after cooling
back to 25 °C, respectively, run at a constant current
density of 10 A/g. A significant reduction in the IR drop
can be observed in the charge⫺discharge curve ob-
tained at 25 °C after cooling from 100 °C compared to
the IR drop in the curve of the as-assembled sample at
25 °C.
To demonstrate the long-term stability of the super-
capacitor, several tens of thousands of charge⫺
discharge cycles were run at different constant current
densities from 100 mA/g (81.46 mA/cm2) to 100 A/g
(81.46 A/cm2) at 25 and 100 °C by repeated heating and
cooling (see Supporting Information S4 for a sequence
of charge⫺discharge measurements and Figure S3 for
some charge⫺discharge measurements at 100 mA/g
and 1 A/g). Figure 4d shows the charge⫺ discharge
curves of the supercapacitor at 100 °C, measured with
constant current density of 100 A/g. The long cycle dis-
charge capacitances of the cell calculated from the gal-
vanostatic charge⫺discharge curves are displayed in
Figure 4e,f. An impressive result of the supercapacitor
is obvious from these measurements. The charge⫺
discharge curves represented ideal capacitive behavior
even at a current density as high as 100 A/g. As the cur-
rent density was very high, large overshoots were ob-
served in the charge⫺discharge curves over 1.5 V. Since
the upper potential of operation for the TEABF4/PC elec-
trolyte system can be as high as 2.5 V,12 the overshoots
did not cause any negative effects such as electrolyte
decomposition or cell failure. This is obvious from the
long cycle performance tested by running over 10 000
charge⫺discharge cycles at 25 and 100 °C both at 50
and 100 A/g (Figure 4f). The slight changes in the slope
of the charge⫺discharge curves lead to variations in
the calculated capacitances (Supporting Information
S5) at high current densities as shown in the Figure 4e,f
(for example, ⬃23 ⫾ 6 F/g at 100 A/g).
Figure 4g shows the plot of specific energy density
versus specific power density, also called a Ragone
plot,39 for the supercapacitor at 25 and 100 °C, respec-
tively. The total weight of the two SWNT film electrodes
was considered in estimating the energy and power
density (Supporting Information S5). The supercapaci-
tor has a maximum power density of about 55 kW/kg at
100 °C obtained with the discharge curve run at a con-
stant current density of 100 A/g. The maximum energy
density obtained from the discharge curve run with 100
mA/g at 100 °C is 4.2 Wh/kg. To obtain an optimum en-
ergy and power density for different applications, the
2204 VOL. 3 ▪ NO. 8 ▪ MASARAPU ET AL.
cell can be operated with a large current density toler-
ance in the temperature range from 25 to 100 °C.
After all the long cycle measurements at different
current densities with repeated heating and cooling,
the cell was run at 25 °C for 246 700 and at 100 °C for ad-
ditional 224 000 charge⫺discharge cycles with a con-
stant current density of 20 A/g. Figure 4h shows the dis-
charge capacitance of all the cycles at both
temperatures. The cell showed excellent ultralong cycle
stability at both 25 and 100 °C with an efficiency of ap-
proximately 82 and 84%, respectively. The efficiency
was calculated based on the degradation in the value
of discharge capacitance after all the charge⫺discharge
cycles (246 700 cycles at 25 °C and 224 000 cycles at
100 °C) from the initial discharge capacitance obtained
from the first charge⫺discharge cycle.
Since supercapacitors are power devices, the most
important figure of merit to be considered is the stabil-
ity of their impedance during the charge⫺discharge cy-
cling with the repeated heating and cooling. Figure 4i
shows the resistance RS of the supercapacitor cell ob-
tained from the EIS measurements at different stages of
the charge⫺discharge measurements (see Supporting
Information S4 for the sequence of charge⫺discharge
measurements carried on the coin cell). There is no sig-
nificant increase in the impedance of the cell even af-
ter running several thousands of charge⫺discharge
cycles at 100 °C, implying a stable power output from
the supercapacitor. It took more than 3 months to per-
form all of the charge⫺discharge measurements with
repeated heating and cooling on the coin cell, and the
cell is still operational. Figure 4 provides strong evi-
dence that the supercapacitor with the free-standing
SWNT film electrodes in TEABF4/PC electrolyte can be
conveniently operated at any current density from 100
mA/g to 100 A/g in the temperature range from 25 to
100 °C with no significant cell damage.
There are several advantages of utilizing the free-
standing SWNT film synthesized from our method32 as
the supercapacitor electrodes. The foremost is that the
SWNT can be handled as an entire film during the whole
process of the synthesis, purification, and electrode
preparation, which is extremely simple compared to
the filtration technique.26 The process can be easily ex-
panded to acquire SWNT film electrodes with uniform
thickness and on a large scale. The complex mixing and
coating procedure27 involved with the powder samples
is not required. The SWNT film itself acts as a good con-
ductor, thus eliminating the usage of the current collec-
tors. By using the supercapacitors with the SWNT film
electrodes and the TEABF4/PC electrolyte, we demon-
strated that the operating temperature can be easily ex-
panded to 100 °C with extremely high rate capability.
CONCLUSIONS
In conclusion, the electrochemical performance of
the coin cell supercapacitor assembled with SWNT film
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electrodes using 1 M TEABF4/PC electrolyte was sys-
tematically studied in a temperature window rang-
ing from 25 to 100 °C. A pseudocapacitive behavior
was observed in the cyclic voltammograms at high
temperature, which was attributed to the physisorb-
tion of the electrolyte ions on the surface of the
SWNTs. Fitting parameters of Nyquist spectra ob-
tained from a modified Randles equivalent circuit re-
vealed that repeated heating and cooling between
25 to 100 °C enhanced the room temperature perfor-
METHODS
Fabrication of the SWNT Macrofilm Electrodes. The SWNT films were
directly deposited on a copper foil by CVD method28 using fer-
rocene as carbon feedstock/catalyst and sulfur as an additive to
promote SWNT growth to a high percentage. There is no addi-
tional carbon source (e.g., xylene, hexane, and methane) required
for the synthesis. The deposited films were peeled off from the
copper foil and were purified by first heating in air up to 450 °C
for 1 h to remove amorphous carbon and then treated in 9 M HCl
solution for 0.5 h to remove the iron catalyst particles. After the
acid treatment, the film was thoroughly washed with DI water.
The purification process did not involve any filtration technique,
and the SWNTs were handled as an entire film through the en-
tire purification process. The complex entanglement of the long
SWNT strands provided strong mechanical stability for the film.
Figure 1a shows a purified SWNT film floating on the water sur-
face. The film was transferred directly from the beaker onto a
wire mesh (loop), as shown in Figure 1b. After drying the film,
two 1.25 cm diameter electrodes were punched with an arch
punch. The photographs of the punched electrodes and the wire
mesh after the electrodes were punched can be seen from Fig-
ure 1c,d. The thickness as well as the weight of the electrodes can
be controlled by varying the number of layers of the SWNT films
deposited on the wire mesh.
Supercapacitor Assembly. The supercapacitor was assembled in
a 2032 coin cell with a pair of SWNT films weighing 0.7 mg each,
without any current collectors. A 1 M TEABF4 (Alfa Aesar) dis-
solved in battery-graded PC (Alfa Aesar) solvent was used as the
electrolyte. A Wattman glass microfiber filter paper soaked in
the electrolyte was used as the separator. The coin cell was
sealed using a Teflon gasket to withstand temperatures up to
150 °C. The supercapacitor assembly was carried out in a glove-
box (MBraun, Unilab) with oxygen and water vapor levels less
than 0.1 ppm. For the temperature-dependent measurements
from 25 up to 100 °C, the coin cell was placed in a box oven (LIN-
BERG/BLUE M) capable of maintaining a very stable set temper-
ature up to one-tenth of a °C. Figure 1e shows the experimental
arrangement of the supercapacitor.
Electrochemical Measurements. The electrochemical characteriza-
tion at different temperatures was done by measuring the cy-
clic voltammograms, electrochemical impedance spectra, and
constant current charge⫺discharge curves. Cyclic voltammo-
grams and the electrochemical impedance spectra of the super-
capacitor were measured with an EG&G Parstat 2273 poten-
tiostat/galvanostat. The galvanostatic charge⫺discharge
examination was carried out by an Arbin battery testing system.
Acknowledgment. This work was financially supported by
the National Science Foundation (NSF CMMI #0753462) and the
Delaware NASA EPSCoR Research Infrastructure Development
(RID) Award.
Supporting Information Available: Cyclic voltammograms of
the coin cell supercapacitor at different temperatures from 25
to 100 °C measured at different scan rates from 50 to 1000 mV/s.
Surface area measurements on purified SWNT macrofilms. Se-
quence of charge⫺discharge measurements carried on the coin
cell at different temperatures. Long cycle charge⫺discharge
www.acsnano.org
ARTICLE
mance of the supercapacitor. The long cycle gal-
vanostatic charge⫺discharge measurements
showed excellent stability in capacitance at both 25
and 100 °C, even at high current densities of 50 and
100 A/g. The stability of the cell was also reflected
under rigorous temperature conditions and the su-
per long galvanostatic charge⫺discharge cycles. The
usage of such a supercapacitor potentially enables
far-reaching advances in civilian, military, and aero-
space applications.
measurements at current densities of 100 mA/g and 1 A/g. This
material is available free of charge via the Internet at http://
pubs.acs.org.
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